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Artigos de revistas sobre o assunto "Chemsitry"
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Bradshaw Editor-in-Chief, Ralph A. "A flavor of protein chemsitry". Trends in Biochemical Sciences 14, n.º 7 (julho de 1989): 243. http://dx.doi.org/10.1016/0968-0004(89)90054-6.
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Sakaki, Shigeyoshi. "Coordination Chemsitry and Theoretical/Computational Studies". Bulletin of Japan Society of Coordination Chemistry 83 (20 de junho de 2024): 64–80. http://dx.doi.org/10.4019/bjscc.83.64.
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Tzalis, Dimitrios, e Yitzhak Tor. "The Organic Chemsitry of Coordination Compounds: Unprecedented Substitution Reactions of Functionalized Polypyridine Complexes". Angewandte Chemie International Edition in English 36, n.º 23 (15 de dezembro de 1997): 2666–68. http://dx.doi.org/10.1002/anie.199726661.
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4
Fitrianti, Nenny, Husna Amalya Melati, Rahmat Rasmawan, Rody Putra Sartika e Lukman Hadi. "Chemsitry Learning Outcomes of 11th Grade Science Students at SMAN 1 Rasau Jaya". Hydrogen: Jurnal Kependidikan Kimia 12, n.º 1 (29 de fevereiro de 2024): 98. http://dx.doi.org/10.33394/hjkk.v12i1.10440.
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This study discusses the ineffective chemistry learning process resulting in poor grades at State Senior High School (SMAN) 1 Rasau Jaya, students tend to receive information from the teacher without constructing their own knowledge, so students have difficulty in constructing the material obtained from the teacher. The purpose of this study is to describe the learning outcomes of students in 11th Grade Science Class odd semester in chemistry subjects at SMAN 1 Rasau Jaya. The form of research used in this research is descriptive research, and the type of research is a case study. Case study is one of qualitative research, in which researchers conduct in-depth exploration of programs, events, processes, activities, for one or more people. The subjects of this study were students of 11th Grade Science Class at SMAN 1 Rasau Jaya in the 2019/2020 school year who took the odd semester general test, totaling 93 students. The research process includes three stages, namely the preparation stage, the implementation stage, and the final stage. The data collection tool used is the odd semester general test score. Results and Discussion regarding Indicator 1: List the general formula of alkane, alkene and alkyne compounds, Indicator 2: Mention the law of conservation of energy, Indicator 3: Determine the number of moles from the results of the experiment, Indicator 4: Determine the value of the equilibrium constant Kc based on the reaction. The results of the general test conducted on 11th Grade students of SMAN 1 Rasau Jaya can be concluded that the learning outcomes of students in the class are not adequate.
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Rahmadhani, Pradita, Sutrisno Sutrisno e Hayuni Retno Widarti. "Implementation of Inquiry based Learning with OE3R Strategy and the Impacts to Students' Conceptual Understanding in Fundamental of Analytical Chemistry". Jurnal Ilmu Pendidikan 26, n.º 2 (20 de dezembro de 2020): 73. http://dx.doi.org/10.17977/um048v26i2p73-77.
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Chemistry created based on process how scientists work and think to understanding a phenomenon or problem that occurs in natural world. That activities gained through physical and mental activities. Discoveries on Science are obtained and solved using inquiry thinking. Many inquiry-based learning strategies have been developed, one of it’s the OE3R (Orientation – Exploration – Explanation – Elaboration - Reflection) Strategy. The purpose of implementation of OE3R strategy on lecturing Fundamental of Analytical Chemistry are to determine effectiveness and differences of students’ conceptual understanding achievements. This research design using a Quasy experiment with pretest and posttest in two groups with different treatment. The Experimental Group learn using OE3R strategy, then the Control Group using conventional strategy based lecturer method. The subject of research was student in Fundamental of Analytical Chemsitry courses at Chemistry Department, Universitas Negeri Malang. The result show that inquiry-based learning with OE3R strategy as innovation learning effective to make differences of students’ conceptual understanding achievements in this courses.
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Eissen, Marco, Juergen O. Metzger, Eberhard Schmidt e Uwe Schneidewind. "ChemInform Abstract: 10 Years After Rio - Concepts on the Contribution of Chemsitry to a Sustainable Development". ChemInform 33, n.º 27 (21 de maio de 2010): no. http://dx.doi.org/10.1002/chin.200227293.
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Arif, Lazaro Sofian, Mawardi Mawardi e Okta Suryani. "Development of Textbooks to Support Mardeka Curriculum Learning on Basic Laws of Chemsitry Materials around Us". Hydrogen: Jurnal Kependidikan Kimia 11, n.º 4 (3 de agosto de 2023): 365. http://dx.doi.org/10.33394/hjkk.v11i4.8312.
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Abstract The objective of this research is to create educational materials for the Mardeka curriculum that focus on fundamental chemical principles. The study adopts the Educational Design Research (EDR) approach, utilizing the plomp development model consisting of three stages: initial investigation, development, and prototype formation. To gather data, validity questionnaires and practicality questionnaires were employed. The developed textbooks underwent validation by five individuals, including three chemistry lecturers from FMIPA UNP and two chemistry teachers from SMAN 8 Padang. Additionally, practicality testing involved nine high school students from Phase E and two chemistry teachers from SMAN 8 Padang. The data analysis employed a Likert scale, employing Aiken's V formula to assess textbook validity and the modified Purwanto formula to assess practicality. The analysis of the data revealed that the product validation by the five validators yielded an average score of 0.86 indicating the textbooks' validity. Furthermore, the practicality evaluation by students and chemistry teachers yielded an average score of 92% and 95% respectively, indicating a high level of practicality. In conclusion, based on the data analysis, it can be inferred that the developed textbooks on the basic chemical laws are both valid and practical for use in chemistry education.
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Al-Badry, Kamal S., Samir El-Deib e Sohir Nuzhy. "Changes in serum chemsitry parameters of the Egyptian cobra (Naja haje haje) in correlation with the hibernation cycle". Journal of Thermal Biology 17, n.º 2 (março de 1992): 111–14. http://dx.doi.org/10.1016/0306-4565(92)90007-3.
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Yamamoto, Masahiro. "K. Kihara, K. Kano, ^|^ldquo;Experts Series for Analytical Chemsitry, Instrumental Analysis: Vol. 12, Electrochemical Analysis^|^rdquo; (in Japanese)". Review of Polarography 58, n.º 2 (2012): 103–4. http://dx.doi.org/10.5189/revpolarography.58.103.
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Primastuti, Metridewi, Erfan Priyambodo e Das Salirawati. "Using Learning Managemant System in Fundamental of Analytical Chemsitry Course: Effect on Students’ Critical Thinking through The Authentic Assessment". TANJAK : Journal of Education and Teaching 4, n.º 2 (22 de agosto de 2023): 73–83. http://dx.doi.org/10.35961/tanjak.v4i2.949.
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Critical thinking is the main skill for connecting relationships between chemical science concepts in a coherent environment. Therefore, a learning and evaluation method is needed to help students master the meaning of chemistry to environmental phenomena. The Fundamental of Analytical Chemistry course invites students to study the technique of determining the concentration of a compound. This is relevant to improve their critical thinking skills. This study aims to analyze the effect of the implementation of Technology-based Authentic Assessment (TbAA) on students' critical thinking skills in Fundamental of Analytical Chemistry course. Designed as a pre-experimental, one group pretest-posttest study was applied. A total of 26 undergraduate Chemistry students were included as samples through purposive sampling. TbAA was held for 7 meetings, then critical thinking skills were assessed through essay instruments covering aspects of interpretation, analysis, evaluation, inference. The validity test was carried out theoretically by 2 learning chemists on 4 critical thinking questions that had been developed. After the data was obtained, descriptive statistics and the Wilcoxon test were carried out to answer the research objectives. Based on the results of the analysis, there is a significant difference in students' critical thinking skills after the application of TbAA.
Teses / dissertações sobre o assunto "Chemsitry"
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Chatare, Vijay K. "METHODOLOGY AND NATURAL PRODUCT SYNTEHSIS: (A) NOVEL GLYCOSYL DONORS; (B) N-SULFINYL METALLODIENAMINES AND THEIR APPLICATION TO THE TOTAL SYNTHESIS OF (–)-ALBOCYCLINE". Diss., Temple University Libraries, 2017. http://cdm16002.contentdm.oclc.org/cdm/ref/collection/p245801coll10/id/456762.
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ChemistryPh.D.
My research involved in two different areas, development of novel glycosylation methodology and scope in oligosaccharide synthesis. A new scaffold for antibiotic development targeting the bacterial cell wall: Total synthesis of Albocycline and its analogs to see the mechanism of action in cell wall biosynthesis. Developed novel gem-dimethyl analogs of Fraser-Reid’s NPGs from 3,3-dimethyl 4-pentenol and 2,2-dimethyl 4-pentenol. These donors are stable toward acidic and basic conditions, which makes them step-efficient when compared to other glycosylating agents. The scope and reactivity of 3,3-dimethyl 4-pentenyl glycosides of glucose, mannose, galactose, and N-acetylglucosamine have been studied extensively for oligosaccharide synthesis. The donors are readily prepared from commercial starting materials and both glycosylation and hydrolysis yields are in the synthetically useful in oligosaccharide synthesis. NSMD methodology introduced a key step in albocycline synthesis, where (‒)-albocycline has great biological activity against “superbug” methicillin-resistant Staphylococcus aureus (MRSA). We hypothesize that albocycline inhibits the first committed step in bacterial cell wall biosynthesis. We have successfully completed two generation syntheses of albocycline. Vinylogous aldol on the left-handed fragment, aldehyde to get selectively up alcohol at the C-8 position using Davis-Ellman sulfinylimine chemistry and then oxidation with Davis oxaziridine to access requisite stereochemistry at C-4 alcohol followed by Horner-Wadsworth-Emmons to access seco-acid. Finally, a Keck macrolactonization reaction provided access to desired (‒)-Albocycline.
Temple University--Theses
2
Mc, Mahon Catherine Niamh. "Modelling of cyclopropene reduction by mo-nitrogenase with iron and platinum chemistry". Thesis, University of Sussex, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.282144.
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Briscoe, Mark William. "Electrochemical reduction of fluorinated systems and derived chemistry". Thesis, Durham University, 1989. http://etheses.dur.ac.uk/6549/.
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The work described in this thesis is divided into four sections: 1. The electrochemical reduction of fluorocarbon derivatives has been investigated. A number of systems have been studied analytically (using cyclic volt amine try) ; whilst preparatively a range of compounds have been synthesised, including semi-conducting polymers and four-membered perfluorocyclic products. 2. The use of sodium amalgam as an electromimetic medium to facilitate reduction of various fluorocarbon substrates has been studied. A series of volatile cyclic and acyclic F-dienes have been prepared from F-alkenes in good yield and conversion. The chemistry of these F-dienes is then described: 3. Both mono- and bi- functional nucleophiles have been reacted, giving a range of novel substitution products. 4. A number of free radical and cycloaddition reactions have been attempted without success. However, the complexation of decamethylferrocene as a metallocene one electron donor, with various F-alkenes of low reduction potential, has allowed a radical anion of a perfluorocyclic-diene to be stabilized and fully characterized for the first time.
4
Waggoner, Sarah Elizabeth. "Effects of repetitive, small magnitude earthquakes on groundwater chemistry in Faulkner County, Arkansas". OpenSIUC, 2011. https://opensiuc.lib.siu.edu/theses/586.
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The drive to find reliable sources of fuel that follow our green concerns and reduce our dependence on foreign sources of fossil fuels has pushed exploration and recovery of natural gas from within the United States to a top priority. Earthquakes generated from the use of hydraulic fracturing techniques and/or use of high pressure injection wells are occurring at an alarming rate due to increases in hydrocarbon exploration and recovery. While the link between earthquakes and hydrocarbon production is still uncertain, earthquake induced changes to groundwater chemistry are clear. Yet it has not been determined if repetitive, smaller earthquakes, i.e. earthquakes with magnitudes less than Mw<4.5, can result in similar disturbances to water chemistry as the more significant events have been proven to cause. Two known earthquake swarms, each having repetitive, small earthquake events, occurred in an intraplate setting in Faulkner County, Arkansas. Testing for groundwater chemical changes related to the timing of earthquake events and total energy released show that small earthquakes indeed create changes to groundwater chemistry most probably due to fluid intrusion from deep, chloride, calcium, and magnesium rich waters. The reduction of the United States dependence on foreign sources or finding green sources of fuel should not be the only mitigating factor for our decisions concerning our natural resources.
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Hashim, Alaa Hassan. "Metallopeptides From Design to Catalysis: Structure, Oxidative Activities, And Inhibition Studies Of Designed And Naturally Occurring Metallopeptides". Scholar Commons, 2014. https://scholarcommons.usf.edu/etd/5626.
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Structural and mechanistic complexities of copper-dioxygen systems have attracted much attention in the field of bioinorganic chemistry, both in model systems and trapped protein intermediates. The research presented herein is focused on model and naturally occurring metallopeptide systems, from its design to catalysis. Copper is used as the coordinating metal ion, with cobalt and zinc as probes for metal binding. The bioinorganic chemistry of copper proteins and its coordination and spectroscopic properties are briefly discussed in chapter 1. The next two chapters are centered on the de novo design of a minimalistic metallopeptide system with an amino acid sequence of RHHPPHHE. Structural characterization of the peptide by means of CD and NMR spectroscopy techniques are presented in chapter 2, suggesting a characteristic beta-turn structure in its apo and di-metal bound form. The designed metallopeptide exhibits catecholase activity, which is presented in chapter 3. The data suggest the presence of two mononuclear copper active sites, exhibiting specificity towards the oxidation of catecholamine substrates. Similarly, the catecholase activity has been previously observed in copper complexes of Alzheimer's disease related peptide beta-amyloid, exhibiting metal-centered redox chemistry. The metallo-(beta-amyloid); complexes are the hallmark Alzheimer's disease and have been attributed to the generation of reactive oxygen species causing oxidative stress. Thus, inhibition of the observed oxidative activities was investigated. Probing the role of phosphate moieties in various compounds as potential inhibitors against the induced oxidative stress is presented in chapter 4. The phosphate analogs of the studied compounds exhibit more pronounced potency, where mutation of the beta amyloid peptide at Arg-5 and Lys-16 give insight into the interactions of the side chains of Arg and Lys with the phosphate moiety. 31P NMR relaxation studies further support the binding/interaction of phosphate with the Cu(II)-(beta-amyloid); complexes. The correlation of phosphate moiety binding/activity will allow for the design of more potent inhibitors toward the Cu(II)-(beta-amyloid); induced oxidative stress.
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Capozzi, Adriana. "Étude des structures chimiques et des propriétés biologiques de polyphénols extraits des parties solides de baies de Vitis vinifera au cours de leur maturation". Electronic Thesis or Diss., Université de Montpellier (2022-....), 2024. http://www.theses.fr/2024UMONG008.
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Le syndrome métabolique (SM) est un ensemble d’altérations métaboliques qui, collectivement, augmentent le risque de maladie cardiaque, d'accident vasculaire cérébral et de diabète de type 2. Il est caractérisé par une tension artérielle élevée, une glycémie élevée, une obésité abdominale et des taux de cholestérol anormaux. L’altération du métabolisme des muscles squelettiques et la résistance à l’insuline jouent un rôle essentiel dans la physiopathologique du SM contribuant de manière significative aux risques associés. Les polyphénols de raisin (GPP) apparaissent comme des candidats prometteurs pour la prise en charge globale du syndrome métabolique. Ils ont montré des effets bénéfiques dans la prise en charge de sujets avec un SM en réduisant l'obésité, la graisse viscérale et en améliorant la sensibilité à l'insuline. Étant donné que la concentration et le type de polyphénols du raisin varient au cours de la maturation et d'un tissu à l'autre, ce travail a étudié l'effet in vitro du stade de maturation du raisin et des tissus sur les activités biologiques d’extraits de raisin Syrah sur le métabolisme de cellules musculaires squelettiques primaires humaines. Nos résultats montrent que les extraits de GPP de la pellicule et des pépins de raisin, quel que soit le stade de maturité, atténuent les altérations induites par le palmitate dans les cellules musculaires stressées, améliorant la biogenèse mitochondriale, les défenses antioxydantes et la réponse insulinique sauf pour les extraits de pépins de raisin vert qui n’améliorent pas la sensibilité à l’insuline. D’un autre côté, les extraits de peau et de pépins de raisin vert caractérisés par une plus grande teneur en polyphénols totaux et à une meilleure capacité antioxydante par rapport aux raisins matures, présentent des effets métaboliques imitant l’exercice sur les cellules musculaires non stressées. Ils améliorent la biogenèse mitochondriale, l’activité métabolique mitochondriale et antioxydante. Pour la première fois, une activité biologique supérieure dans l'amélioration de la fonction métabolique des cellules musculaires squelettiques humaines a été démontrée avec les polyphénols de raisin vert, contrastant avec les effets généralement décrits des polyphénols de raisin au stade mûrMetabolic syndrome (MS) is a cluster of conditions that collectively heighten the risk of heart disease, stroke, and type 2 diabetes, characterized by elevated blood pressure, high blood sugar, abdominal obesity, and abnormal cholesterol levels. Altered skeletal muscle metabolism and insulin resistance are pivotal in its physiopathology, contributing significantly to associated health risks. Grape polyphenols (GPP) emerge as promising candidates for the global management of MS since they have shown promise in addressing these complexities by reducing obesity, visceral fat, and enhancing insulin sensitivity. Since grape polyphenol concentration and type vary during ripening and from tissue to tissue, this work investigated the effect in vitro of grape ripening stage and tissue on the biological activities of Syrah GPP extracts on the metabolism of human skeletal muscle cells. Our findings highlight that GPP extracts from grape skin and seeds, regardless of maturity stage, mitigate palmitate-induced alterations in stressed muscle cells, enhancing mitochondrial biogenesis, antioxidant defenses and insulin response except green grape seeds extract which don’t improve insulin sensitivity. On the other side, only extracts from green grape skin and seeds exhibit exercise-mimicking effects in unstressed muscle cells, enhancing mitochondrial biogenesis, metabolic activity and antioxidant capacity, also related to their higher total polyphenol content and antioxidant capacity. For the first time, superior biological activity in enhancing metabolic function of human skeletal muscle cells has been demonstrated with green grape polyphenols, contrasting with the typically described effects of mature grape polyphenols
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Pearcy, Adam C. "Non-covalent and covalent interactions between phenylacetylene and quinoline radical cations with polar and non-polar molecules in the gas phase". VCU Scholars Compass, 2019. https://scholarscompass.vcu.edu/etd/5990.
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Gas phase molecular clusters present an ideal medium for observing factors that drive chemical reactions without outside interferences from excessive solvent molecules. Introducing an ion into the cluster promotes ion-molecule interactions that may manifest in a variety of non-covalent or even covalent binding motifs and are of significant importance in many fields including atmospheric and astronomical sciences. For instance, in outer space, molecules are subject to ionizing radiation where ion-molecule reactions become increasingly competitive to molecule-molecule interactions. To elucidate individual ion-molecule interaction information, mass spectrometry was used in conjunction with appropriate theoretical calculations.
Three main categories of experiment were conducted in this dissertation. The first of which were thermochemical equilibrium measurements where an ion was introduced to an ion mobility drift cell wherein thermalizing collisions occur with helium buffer gas facilitating a reversible reaction with a neutral molecule allowing the standard changes in enthalpy and entropy to be determined. The second type of experiment was an ion mobility experiment where an ionized homo- or hetero-cluster was injected into the drift cell at specific conditions allowing the reduced mobility and collisional cross-section to be evaluated. Thirdly, kinetics measurements were taken following injection of an ion into the drift cell were an irreversible reaction ensued with the neutral species hindering equilibrium, but prompting rate constant assessment.
Previous research has laid the groundwork for this dissertation as the results and discussion contained herein will build upon existing data while maintaining originality. For example, past work has given support for ion-molecule reactions involving precursor species such as acetylene and hydrogen cyanide to form more complex organics, perhaps leading to biologically relevant species. The chemical systems studied for this research are either ionized substituted benzenes like phenylacetylene and benzonitrile or polycyclic aromatic nitrogen-containing hydrocarbons like quinoline and quinoxaline interacting with a variety of neutral species.
Hydrogen bonding and its many sub-sections are of the utmost importance to the kinds of reactions studied here. Past work has shown the tendency of organic radical cations to form conventional and unconventional ionic hydrogen bonds with gas phase solvents. Other non-covalent modes of interaction have also been detected in addition to the formation of covalently bound species. Gas phase reactions studied here will explore, via mass-selected ion mobility, reversible and irreversible reactions leading to binding enthalpy and entropy and rate constant determination, respectively, in addition to collisional cross-section determination.
8
Noureddine, Achraf. "Approches Click en Chimie Sol-Gel". Thesis, Montpellier, Ecole nationale supérieure de chimie, 2014. http://www.theses.fr/2014ENCM0005/document.
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Nous visons dans ce travail de thèse à développer une méthodologie de fonctionnalisation par chimie click des silices hybrides synthétisées par voie sol-gel. La réaction click de cycloaddition azoture-alcyne catalysée au cuivre (CuAAC) offre une tolérance exceptionnelle pour les fonctions organiques en plus de conversions très élevées. Dans cette optique, nous avons mis en œuvre en premier lieu des matériaux clickables à base d'organosilice pure (organosilice à mésoporosité périodique (PMO) et silsesquioxanes pontés (BS)) qui ont permis une conversion quasi-quantitative de greffage par CuAAC. Nous avons ensuite utilisé cette particularité pour contrôler les propriétés de surface des BS en modifiant leur caractère hydrophile/lipophile. Dans le second axe de travail, nous nous sommes intéressés à l'apport de la chimie click pour la préparation de nanoparticules mésoporeuses de silice multifonctionnelles, dites mécanisées, pour des systèmes à délivrance contrôlée de principes actifsThe present work aims to develop a trustful methodology of functionalization for hybrid silica materials made by the sol-gel process using the copper-catalyzed alkyne-azide cycloaddition (CuAAC)Click reaction. This transformation can be highly useful in materials science thanks to its high conversions and the excellent functional group tolerance. In this prospect, we have synthesized fully clickable bridged silisesquioxanes and periodic mesoporous organosilica that show high extents of click grafting. CuAAC was then used for tailoring the surface of bridged silsesquioxane and fine-tuning the hydrophilic/lipophilic balance. Finally, the click reaction was used as an efficient way to obtain multiply functionalized mesoporous silica nanoparticles in order to make nanomachines for controlled delivery of cargo molecules
9
Ramesh, R. "Studies On The Chemistry Of Carbonates And Carbamates". Thesis, 2007. https://etd.iisc.ac.in/handle/2005/2256.
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The thesis entitled ‘Studies on the Chemistry of Carbonates and Carbamates’ comprises of seven chapters.
Chapter 1
The reactivity of propargyloxycarbonyl (Poc) derivatives of amines and alcohols with various sulphur nucleophiles is addressed in this chapter. The chapter is divided into three different parts.
Part 1: The difference in reactivity of propargyloxycarbonyl (Poc) derivatives of amines and alcohols with benzyltriethylammonium tetrathiomolybdate [(PhCH2NEt3)2MoS4, 1] is studied in detail and the results are discussed. It has been shown that amino alcohols can be protected as their diPoc derivatives using 2 equiv of propargyloxycarbonyl chloride (2). The selective deprotection of the O-Poc group using 1 equiv of 1 without affecting the N-Poc group is achieved (Scheme 1).
Scheme 1
Part 2: The reactivity of propargyloxycarbonyl derivatives of various alcohols, phenols and primary and secondary amines with benzyltriethylammonium tetrathiomolybdate (1) is compared with the reactivity of these Poc derivatives with other sulphur nucleophiles such as sodium thiophenoxide, lithium sulphide, hydrogen sulphide and ammonium sulphide. The study reveals that tetrathiomolybdate (1) is the best sulphur nucleophile for the deprotection of Poc group. Poc derivatives of primary amines cyclized to the corresponding 4-methylene-2-oxazolidinones when treated with other sulphur nucleophiles (Scheme 2).
Scheme 2
Part 3: The reaction between different propargyloxycarbonyl derivatives of alcohols and benzyltriethylammonium tetrathiomolybdate (1) is studied. It is found that propargyloxycarbonyl derivatives can be made more reactive towards tetrathiomolybdate by substituting the propargyl system with electron withdrawing substituents.
Chapter 2
The application of propargyloxycarbonyl group for the protection of the side chain hydroxyl groups of serine, threonine and tyrosine is discussed. The O-Poc derivatives are shown to be stable to a variety of acidic and basic conditions and the applications of these derivatives in solution phase peptide synthesis is addressed. The easy and effective deprotection of the O-Poc group provides a new strategy for the synthesis of peptides bearing the hydroxy amino acid residues: serine, threonine and tyrosine.
Scheme 3
Chapter 3
Development of a novel C2-symmetric protecting group for amines and amino acids is described in this chapter. But-2-ynyl-1,4-bisoxycarbonyl chloride (BbcCl, 3) is synthesized from 1,4-dihydroxybut-2-yne and used as a reagent for protecting amines as biscarbamates (Scheme 4). These biscarbamates (Bbc derivatives) are deblocked using benzyltriethylammonium tetrathiomolybdate (1) to get the amines back.
Scheme 4
The orthogonal stability of the Bbc group with Boc, Cbz and Fmoc groups is established. It is also shown that Bbc group can be deblocked to the corresponding amines using resin-bound tetrathiomolybdate. The application of Bbc protected amino acids in solution phase peptide synthesis is demonstrated (Scheme 5).
Scheme 5
Chapter 4
The simultaneous protection and activation of amino acids using various pentafluorophenyl carbonates is described in two parts.
Part 1: A very efficient and high yielding method for the simultaneous protection of the amino group and activation of carboxylic acid group using propargyl pentafluorophenyl carbonate (PocOPfp, 4) is discussed. Treating amino acids with 2 equiv of 4 protects the amino group as a propargyl carbamate and activates the carboxylic acid group as a pentafluorophenyl ester (Scheme 6).
Scheme 6
Part 2: The generality of the methodology developed for the simultaneous protection and activation of amino acids using PocOPfp (4) is studied with five different pentafluorophenyl carbonates viz. AlocOPfp, CbzOPfp, BocOPfp, EocOPfp and TrocOPfp. The studies reveal that the effectiveness of the methodology depends on the nature of the pentafluorophenyl carbonates and on the nature of the amino acids. Sterically bulky pentafluorophenyl carbonates such as BocOPfp reacted slowly with amino acids while electron deficient pentafluorophenyl carbonates such as TrocOPfp reacted faster and gave the N-protected active esters in very good yields. Amino acids bearing longer aliphatic side chains reacted better than the other amino acids.
Chapter 5
The chapter describes results of the detailed studies on the base catalyzed cyclization of N-alkyl and N-aryl-O-propargyl carbamates to the corresponding 4-alkylidene-2-oxazolidinones. The effect of various bases and solvents on these cyclization reactions is studied systematically to design the most suitable conditions. The best results were obtained using catalytic amount of LiOH in DMF. The cyclization reactions of N-aryl-O-propargyl carbamates were faster than the cyclization of N-alkyl-O-propargyl carbamates. The effect of substitutions on the propargyl group in these reactions is studied by preparing various substituted propargyl carbamate derivatives from the corresponding amines and propargyl chloroformates (Scheme 7).
Scheme 7
Chapter 6
An efficient procedure for the synthesis of dehydroalanine and dehydroamino butyric acid derivatives from the preformed carbonate derivatives of serine and threonine respectively, by treating with K2CO3 in DMF is discussed in this chapter. The reaction proceeds stereoselectively through a trans E2-elimination pathway to give only the Z-isomer of dehydroamino butyric acid derivatives from the carbonate derivatives of threonine. The methodology offers an easy access to dehydropeptides and proceeds without racemization of other stereogenic centers present in the peptide (Scheme 8).
Scheme 8
Chapter 7
This chapter describes the use of propargyloxycarbonyl derivatives of lysine as an efficient tool for the synthesis of peptide conjugates using a click chemistry approach. The Cu(I) catalyzed cycloaddition reaction between azides and alkynes is employed in the synthesis of conjugates of lysine. Peptides bearing an Nε-Poc Lysine residue can be synthesized using traditional strategies and these peptides can be easily conjugated with azide derivatives of sugars and amino acids (Scheme 9).
Scheme 9
The efficiency of the method is demonstrated by carrying out more than one click reaction in one pot using di and tri-propargyl derivatives of lysine. A dendritic core (6) is prepared from a tri-propargyl derivative (5) of lysine and an azide derived from leucine (Scheme 10).
Scheme 10
The abbreviations used in the thesis are consistent with those reported in J. Org. Chem. 2007, 71, 23A. Less common abbreviations are defined, the first time they are mentioned in the thesis.
10
Ramesh, R. "Studies On The Chemistry Of Carbonates And Carbamates". Thesis, 2007. http://etd.iisc.ernet.in/handle/2005/2256.
Texto completo da fonteResumo:
The thesis entitled ‘Studies on the Chemistry of Carbonates and Carbamates’ comprises of seven chapters.
Chapter 1
The reactivity of propargyloxycarbonyl (Poc) derivatives of amines and alcohols with various sulphur nucleophiles is addressed in this chapter. The chapter is divided into three different parts.
Part 1: The difference in reactivity of propargyloxycarbonyl (Poc) derivatives of amines and alcohols with benzyltriethylammonium tetrathiomolybdate [(PhCH2NEt3)2MoS4, 1] is studied in detail and the results are discussed. It has been shown that amino alcohols can be protected as their diPoc derivatives using 2 equiv of propargyloxycarbonyl chloride (2). The selective deprotection of the O-Poc group using 1 equiv of 1 without affecting the N-Poc group is achieved (Scheme 1).
Scheme 1
Part 2: The reactivity of propargyloxycarbonyl derivatives of various alcohols, phenols and primary and secondary amines with benzyltriethylammonium tetrathiomolybdate (1) is compared with the reactivity of these Poc derivatives with other sulphur nucleophiles such as sodium thiophenoxide, lithium sulphide, hydrogen sulphide and ammonium sulphide. The study reveals that tetrathiomolybdate (1) is the best sulphur nucleophile for the deprotection of Poc group. Poc derivatives of primary amines cyclized to the corresponding 4-methylene-2-oxazolidinones when treated with other sulphur nucleophiles (Scheme 2).
Scheme 2
Part 3: The reaction between different propargyloxycarbonyl derivatives of alcohols and benzyltriethylammonium tetrathiomolybdate (1) is studied. It is found that propargyloxycarbonyl derivatives can be made more reactive towards tetrathiomolybdate by substituting the propargyl system with electron withdrawing substituents.
Chapter 2
The application of propargyloxycarbonyl group for the protection of the side chain hydroxyl groups of serine, threonine and tyrosine is discussed. The O-Poc derivatives are shown to be stable to a variety of acidic and basic conditions and the applications of these derivatives in solution phase peptide synthesis is addressed. The easy and effective deprotection of the O-Poc group provides a new strategy for the synthesis of peptides bearing the hydroxy amino acid residues: serine, threonine and tyrosine.
Scheme 3
Chapter 3
Development of a novel C2-symmetric protecting group for amines and amino acids is described in this chapter. But-2-ynyl-1,4-bisoxycarbonyl chloride (BbcCl, 3) is synthesized from 1,4-dihydroxybut-2-yne and used as a reagent for protecting amines as biscarbamates (Scheme 4). These biscarbamates (Bbc derivatives) are deblocked using benzyltriethylammonium tetrathiomolybdate (1) to get the amines back.
Scheme 4
The orthogonal stability of the Bbc group with Boc, Cbz and Fmoc groups is established. It is also shown that Bbc group can be deblocked to the corresponding amines using resin-bound tetrathiomolybdate. The application of Bbc protected amino acids in solution phase peptide synthesis is demonstrated (Scheme 5).
Scheme 5
Chapter 4
The simultaneous protection and activation of amino acids using various pentafluorophenyl carbonates is described in two parts.
Part 1: A very efficient and high yielding method for the simultaneous protection of the amino group and activation of carboxylic acid group using propargyl pentafluorophenyl carbonate (PocOPfp, 4) is discussed. Treating amino acids with 2 equiv of 4 protects the amino group as a propargyl carbamate and activates the carboxylic acid group as a pentafluorophenyl ester (Scheme 6).
Scheme 6
Part 2: The generality of the methodology developed for the simultaneous protection and activation of amino acids using PocOPfp (4) is studied with five different pentafluorophenyl carbonates viz. AlocOPfp, CbzOPfp, BocOPfp, EocOPfp and TrocOPfp. The studies reveal that the effectiveness of the methodology depends on the nature of the pentafluorophenyl carbonates and on the nature of the amino acids. Sterically bulky pentafluorophenyl carbonates such as BocOPfp reacted slowly with amino acids while electron deficient pentafluorophenyl carbonates such as TrocOPfp reacted faster and gave the N-protected active esters in very good yields. Amino acids bearing longer aliphatic side chains reacted better than the other amino acids.
Chapter 5
The chapter describes results of the detailed studies on the base catalyzed cyclization of N-alkyl and N-aryl-O-propargyl carbamates to the corresponding 4-alkylidene-2-oxazolidinones. The effect of various bases and solvents on these cyclization reactions is studied systematically to design the most suitable conditions. The best results were obtained using catalytic amount of LiOH in DMF. The cyclization reactions of N-aryl-O-propargyl carbamates were faster than the cyclization of N-alkyl-O-propargyl carbamates. The effect of substitutions on the propargyl group in these reactions is studied by preparing various substituted propargyl carbamate derivatives from the corresponding amines and propargyl chloroformates (Scheme 7).
Scheme 7
Chapter 6
An efficient procedure for the synthesis of dehydroalanine and dehydroamino butyric acid derivatives from the preformed carbonate derivatives of serine and threonine respectively, by treating with K2CO3 in DMF is discussed in this chapter. The reaction proceeds stereoselectively through a trans E2-elimination pathway to give only the Z-isomer of dehydroamino butyric acid derivatives from the carbonate derivatives of threonine. The methodology offers an easy access to dehydropeptides and proceeds without racemization of other stereogenic centers present in the peptide (Scheme 8).
Scheme 8
Chapter 7
This chapter describes the use of propargyloxycarbonyl derivatives of lysine as an efficient tool for the synthesis of peptide conjugates using a click chemistry approach. The Cu(I) catalyzed cycloaddition reaction between azides and alkynes is employed in the synthesis of conjugates of lysine. Peptides bearing an Nε-Poc Lysine residue can be synthesized using traditional strategies and these peptides can be easily conjugated with azide derivatives of sugars and amino acids (Scheme 9).
Scheme 9
The efficiency of the method is demonstrated by carrying out more than one click reaction in one pot using di and tri-propargyl derivatives of lysine. A dendritic core (6) is prepared from a tri-propargyl derivative (5) of lysine and an azide derived from leucine (Scheme 10).
Scheme 10
The abbreviations used in the thesis are consistent with those reported in J. Org. Chem. 2007, 71, 23A. Less common abbreviations are defined, the first time they are mentioned in the thesis.
Livros sobre o assunto "Chemsitry"
1
Laird, Brian B. University chemistry. Dubuque, IA: McGraw-Hill, 2008.
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2
El-Basil, Sherif. Combinatorial organic chemistry: An educational approach. New York: Nova Science Publishers, 1999.
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3
Olmsted. Chemsitry. Wiley & Sons, Incorporated, John, 2002.
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4
Zubrick, James W. Organic Chemsitry. Wiley & Sons, Incorporated, John, 2013.
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5
Sutcliffe, Brian T., e Graham Doggett. Mathematics for Chemsitry. Longman Publishing Group, 1995.
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6
General Chemsitry Lab I, 8E: CHEM 141. Academx Publishing Services, Incorporated, 2022.
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7
Simpson, Pam. General Chemsitry Lab I, 7E - CHEM 141. Academx Publishing Services, Incorporated, 2021.
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8
CC, Brightpoint. General Chemsitry II LM, 10E - CHE 112. Academx Publishing Services, Incorporated, 2022.
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9
Inquiry Into Chemsitry Laboratory Manual: Teacher Edition. Glencoe, 2009.
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10
Baird, Colin. Environmental Chemsitry/SM: Science of Biology 4e/Im. W.H. Freeman & Company, 1995.
Encontre o texto completo da fonteTrabalhos de conferências sobre o assunto "Chemsitry"
1
Giroux, Jacques G., Marc-Andre A. Soucy, Francois Chateauneuf e Victor A. Wehrle. "Design of the Atmospheric Chemsitry Experiment instrument". In International Symposium on Optical Science and Technology, editado por Marija Strojnik e Bjorn F. Andresen. SPIE, 2000. http://dx.doi.org/10.1117/12.406556.
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2
Tian, Qing-wei. "Analysis and Assessment of Physical Chemsitry Examination Proposition with Educational Measurement". In 2018 International Conference on Education Reform and Management Science (ERMS 2018). Paris, France: Atlantis Press, 2018. http://dx.doi.org/10.2991/erms-18.2018.75.
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3
Arlianty, Widinda Normalia, Beta Wulan Febriana e Artina Diniaty. "An analysis of learning process based on scientific approach in physical chemsitry experiment". In PROCEEDINGS FROM THE 14TH INTERNATIONAL SYMPOSIUM ON THERAPEUTIC ULTRASOUND. Author(s), 2017. http://dx.doi.org/10.1063/1.4978157.
Texto completo da fonteRelatórios de organizações sobre o assunto "Chemsitry"
1
Roger Atkinson e Janet Arey. Studies of the Atmospheric Chemsitry of Energy-Related Volatile Organic Compounds and of their Atmospheric Reaction Products. Office of Scientific and Technical Information (OSTI), abril de 2007. http://dx.doi.org/10.2172/902099.
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